Diphenoxymethylpyridines and compositions containing same having herbicidal properties

ABSTRACT

Disclosed are diphenoxymethyl pyridines, their preparation and their use as herbicides.

CROSS REFERENCE TO RELATED APPLICATION

This is a division of application Ser. No. 656,834, filed Oct. 2, 1984,now U.S. Pat. No. 4,606,757 issued Aug. 19, 1986, which is acontinuation-in-part of application Ser. No. 452,584, filed Dec. 23,1982 and now abandoned.

SUMMARY OF THE INVENTION

The present invention is directed to compounds corresponding to theformula ##STR1## wherein R represents hydrogen, alkyl of 1 to 4 carbonatoms, hydroxyalkoxy of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbonatoms, alkenyloxy of 2 to 4 carbon atoms, alkylthio of 1 to 4 carbonatoms, alkoxyalkoxy wherein each alkoxy group independently containsfrom 1 to 4 carbon atoms, chloro or fluoroalkoxy of 1 to 4 carbon atoms,cyano, aminomethyl, monoalkylamino of 1 to 4 carbon atoms, dialkylaminowith each alkyl group independently being of 1 to 4 carbon atoms,piperidinyl, morpholino, the radical ##STR2## wherein A is oxygen orsulfur and R¹ is alkyl of 1 to 4 carbon atoms or R represents triazolylor the radical ##STR3## wherein R² is hydrogen or alkyl of 1 to 4 carbonatoms; X represents bromo, chloro or fluoro; n represents an integer of0 or 1 with the proviso that when R is hydrogen, n is 0; Z representsbromo, chloro, fluoro, alkylthio of 1 to 4 carbon atoms or alkoxy of 1to 4 carbon atoms and m represents an integer of 0 or 1.

In the present specification and claims, the terms "alkyl" and "alkoxy"as employed in the terms alkyl, alkoxy, alkylthio, fluoroalkoxy,alkoxyalkoxy monoalkylamino and dialkylamino designate straight-chain,branched-chain or cyclic alkyl groups.

The terms "chloroalkoxy" and "fluoroalkoxy" as employed in the presentspecification and claims designates an alkyl group as defined abovewhich is substituted with from 1 chloro or fluoro atom up to perchloroor perfluoro substitutions.

The term "halo" as employed in the present specification and claimsdesignates either bromo, chloro or fluoro.

The substituted pyridine compounds of the employed present invention areeither solids or liquids which are only slightly soluble in water andare usually moderately to highly soluble in common organic solvents. Thecompounds of the present invention have been found to be very effectivepre- and/or post-emergent herbicides for the control of one or moreplant species.

The compounds of the present invention can be prepared by a variety ofmethods. For example, those compounds wherein R is hydrogen can beprepared by the catalytic hydrogenation of an appropriate6-halo-2-(diphenoxy or substituted diphenoxy)methyl)pyridine in thepresence of a solvent.

While any suitable hydrogenation procedure can be employed in carryingout this hydrogenation reaction, it is convenient to mix a catalyticamount of from about 0.1 to about 10 percent by weight of the catalyst,the pyridine reactant, a solvent and an HCl absorber together and thenpass hydrogen into the mixture. It is also convenient to use a sealedreaction vessel.

Representative catalyst include any of the conventional hydrogenationcatalyst such as platinum or palladium on charcoal. Representativesolvents include ethanol, methanol, toluene or ethyl acetate.

The reaction is usually carried out at a temperature of from about 15°C. to about 30° C. and at a pressure in the range of from about 50 psig.The reaction is usually complete in from about 3 to about 8 hours.

After the reaction is complete, the reaction mixture is filtered toremove the catalyst and other insolubles and then concentrated byevaporation of the solvent under reduced pressure. The concentrate ismixed with dilute sodium hydroxide and extracted with a solvent such asmethylene chloride, ether, methylchloroform or chloroform. The extractis washed with water dried and the solvent removed by conventionaltechniques such as decantation or evaporation. The crude product whichremains is distilled to remove lower boiling impurities and recoveringthe desired product.

Those compounds wherein R is alkyl, alkoxy or cyano can be prepared bythe reaction of one mole of the appropriate 6-alkyl, 6-alkoxy or6-cyano-2-(dichloromethyl)pyridine is reacted with 2 moles of theappropriate phenol in the presence of a solvent and an alkali metalhydroxide such as the sodium, potassium, lithium or cesium hydroxide.The reaction scheme is as follows: ##STR4##

In the above, R is alkyl, alkoxy or cyano and X, Z, n and m are ashereinbefore defined. No attempt has been made to present a balancedequation.

In carrying out this reaction, the pyridine reactant and the salt of thephenol are mixed together in the presence of a solvent and heated to atemperature of from about 100° to about 200° C. and stirred for fromabout 2 to about 24 hours. Thereafter, the reaction product is cooled,diluted with water and extracted with a solvent such as for example,1,1,1-trichloroethane, methylene chloride, chloroform, ethyl acetate orethyl ether. The solvent extract is water washed, dried and concentratedunder reduced pressure and if desired, purified by distillation or otherconventional methods.

The reaction consumes the reactants in stoichiometric proportions, i.e.one molar equivalent of the pyridine reactant to 3 molar equivalents ofthe phenol reactant. However, due to the nature of the reaction, it ispreferred that a 5 to 25 percent excess of the phenol reactant beemployed.

While the above procedure shows the use of an already prepared alkalimetal salt of the phenol, this salt can be prepared in situ. In such aprocedure, the pyridine reactant, an appropriate substituted methoxyphenol and an alkali metal hydroxide are mixed together with the solventand then heated as set forth hereinabove. The alkali metal hydroxide isemployed in a molar amount equal to that employed for the phenolreactant.

Representative solvents for use in carrying out this reaction includedimethyl sulfoxide dimethylformamide, N-methyl-2-pyrrolidone, tolueneand xylene.

Those compounds wherein R is alkoxy, hydroxyalkoxy, alkoxyalkoxy,fluoroalkoxy or alkylthio can be prepared by the reaction of anappropriate 6-halo-2-((diphenoxy or substituted phenoxy)methyl)pyridinewith an appropriate alcohol or thioalcohol in the presence of a solventand a base. The reaction scheme is as follows: ##STR5##

In the above X, Z, n and m are as hereinabove defined and R³ is alkoxy,hydroxyalkoxy, alkoxyalkoxy, or alkylthio. Additionally, no attempt hasbeen made to present a balanced equation.

In carrying out the reaction, the reactants can be mixed in any suitablefashion. Usually, the R³ --H reactant is mixed with the base and thepyridine reactant, in the solvent, is added thereto.

Representative solvents which can be employed in the reaction includedimethylsulfoxide (DMSO), sulfolane, dimethylformamide (DMF) anddioxane.

Representative bases which can be employed include the metal, hydroxideor hydrides of sodium or potassium. The reaction is carried out byheating the mixture at a temperature in the range of from about 25° toabout 100° C. for from about 16 hours to about 24 hours or more.

At the completion of the reaction, the reaction mixture is poured intowater or a water-alcohol mixture and then extracted with a solvent suchas methylene chloride, methylchloroform, ether or chloroform. Thesolvent/organic layer is separated and washed with water, dried,filtered to remove insolubles and the solvent removed by evaporationunder reduced pressure. The product is then recovered by distillation.

The reaction consumes the reactants in stoichiometric proportions, i.e.,one molar equivalent of the pyridine reactant to one molar equivalent ofthe R³ --H reactant. However, due to the nature of the reaction it ispreferred that a 5 to a 100 percent excess of the R³ --H reactant beemployed. The base is employed in an amount of 1.0 to 1.2 molarequivalents per equivalent of the alcohol or thio alcohol.

Those compounds wherein R is alkenyloxy can be prepared by the reactionof an appropriate 6-hydroxy-2-di-(phenoxy or substitutedphenoxy)pyridine with an alkenylhalide in the presence of a solvent andan alkali metal hydrogen halide absorber.

In carrying out this reaction, it is convenient to first mix thehydroxypyridine reactant with an alkali metal hydride such as sodiumhydride at room temperature in a solvent such as dimethylsulfoxide,sulfolane, dioxane or dimethylformamide to convert the hydroxy group tothe reactive NaO-- group. The alkenyl halide is then slowly added, withstirring. The reaction is usually complete in from about 1 to about 2hours. After the completion of the reaction, the reaction mixture isdiluted with water and extracted with a solvent such as methylenechloride, chloroform, methylchloroform or ether. The extract is driedand the solvent is removed. The product can be recovered from theresidue by conventional techniques such as distillation under reducedpressure.

The reaction consumes the reactants in stoichiometric proportions, i.e.,one molar equivalent of the pyridine reactant to one molar equivalent ofthe alkenyl halide reactant. However, due to the nature of the reactionit is preferred that a 5 to a 100 percent excess of the alkenyl halidereactant be employed. The base is employed in an amount of 1.0 to 1.3molar equivalents per equivalent of the pyridine reactant.

Those compounds wherein R is chloro or fluoroalkoxy or ##STR6## can beprepared by the reaction of an appropriate 6-hydroxy(ormercapto)-2-((diphenoxy or substituted diphenoxy)methyl)pyridine with anappropriate R⁴ --Cl (or Br) compound wherein R⁴ is chloro or fluoroalkoxy or a propionic acid ester in the presence of a solvent and abase. The reaction procedure, the base and the solvent are the same asset forth above. The reaction scheme is as follows: ##STR7##

In carrying out the reaction, the reactants can be mixed in any suitablefashion. Usually the pyridine reactant in solvent is mixed with thealkali metal hydride to convert the hydroxy group to the reactive NaO--group. the bromo (or chloro) --R⁴ reactant is then added. The reactionis usually complete in from about 1 to about 4 hours. After thecompletion of the reaction, the reaction mixture is diluted with waterand extracted with a solvent such as methylene chloride, ether,methylchloroform or chloroform. The extract is dried and the solvent isremoved. The product can be recovered from the residue by conventionaltechniques such as distillation under reduced pressure.

The reaction consumes the reactants in stoichiometric proportions, i.e.,one molar equivalent of the pyridine reactant to one molar equivalent ofthe propionate reactant. However, due to the nature of the reaction itis preferred that a 5 to a 100 percent excess of the propionate reactantbe employed. The base is employed in an amount of 1.0 to 1.2 molarequivalents per equivalent of the pyridine reactant.

The acid form of the compound is prepared by conventional procedureswherein the ester is reacted with 50% caustic in a solvent and thenacidified with an acid such as concentrated hydrochloric acid.

Those compounds wherein R is monoalkylamino, dialkylamino, piperidinyl,morpholino or triazolyl can be prepared by the reaction of anappropriate 6-chloro-2-((diphenoxy or substituteddiphenoxy)methyl)pyridine with an appropriate R⁵ --H compound wherein R⁵is monoalkylamino, dialkylamino, piperidinyl, morpholino or triazolyl ata temperature of from about 50° C. to the reflux temperature of themixture. While the reaction can be carried out neat, it can also becarried out in the presence of a solvent such as dimethylsulfoxide,sulfolane, dimethylformamide or dioxane. In addition, an alkali metalhydride such as sodium hydride can be employed to act as a hydrogenchloride absorber.

At the completion of the reaction, the reaction mixture is cooled andmixed with water and a solvent such as methylene chloride,methylchloroform, ether or chloroform. The solvent/organic layer isseparated dried and filtered to remove insolubles and the solventremoved by evaporation under reduced pressure. The product is thenrecovered by distillation and if desired, it can be further purified byrecrystallization from a solvent such as n-hexane or methylene chloride.

Those compounds wherein R is aminomethyl can be preparred by thereduction of an appropriate 6-cyano-2-((diphenoxy or substituteddiphenoxy)methyl)pyridine to the corresponding6-aminomethyl-2-((diphenoxy or substituted diphenoxy)methyl)pyridineemploying a reducing agent such as for example lithium aluminum hydride.The reduction is carried out in the presence of a solvent and under anoxygen free atmosphere such as achieved by using nitrogen gas.

At the completion of the reaction, the reaction mixture is mixed withdilute caustic and filtered. The solvent/organic layer is separated andwashed with ether, dried, and the solvent removed by evaporation underreduced pressure. The resulting material can be further purified byadmixture with a solvent such as methylene chloride, methylchloroform,ether or chloroform. The solvent/organic layer is filtered and thesolvent removed by evaporation under reduced pressure leaving thedesired product.

The reaction consumes the reactants in stoichiometric proportions, i.e.,one molar equivalent of the pyridine reactant to one molar equivalent ofthe reducing agent. However, due to the nature of the reaction it ispreferred that a 1 to a 50 percent excess of the reducing agent beemployed.

Those compounds wherein R is the radical ##STR8## can be prepared by thereaction of an appropriate 6-hydroxy-2-((diphenoxy or substituteddiphenoxy)methyl)pyridine with an appropriate chlorophosphorous compoundof the formula ##STR9## in the presence of an alkali metal compound suchas sodium or potassium hydroxide or carbonate and a solvent.Representative solvents include acetone, acetonitrile,dimethylformamide, carbon tetrachloride, chloroform, benzene, toluene,isobutylmethylketone or melthylene chloride.

The amounts of the reactants to be employed are not critical, some ofthe desired product being obtained when employing any proportions of thereactants. In the preferred method of operation, good results areobtained when employing substantially equimolar proportions of thepyridine and phosphorus reactants.

The reaction takes place smoothly at temperatures in the range of fromabout 0° to about 100° C. In carrying out the reaction, the reactantsare mixed and contacted together in any convenient fashion and theresulting mixture maintained for a period of from about 3 to about 16hours to complete the reaction. Following the completion of thereaction, the solvent is removed by conventional techniques such asdecantation or evaporation under reduced pressure. The residue isfurther purified by taking the residue up in a solvent such as ether,methylene chloride or methylchloroform. The mixture is filtered toremove insolubles, washed with dilute sodium hydroxide and then withwater. The organic layer is separated, dried and the solvent removed byconventional techniques leaving the desired product.

DESCRIPTION OF SOME PREFERRED EMBODIMENTS

The following examples illustrate the present invention and the mannerby which it can be practical but, as such, should not be construed aslimitations upon the overall scope of the same.

EXAMPLE I 2-(Diphenoxymethyl)pyridine ##STR10##

To a solution of 10.42 grams (g) (0.032 mole (m)) of6-chloro-2-(diphenoxymethyl)pyridine, 8.02 g (0.079 m) of triethylaminein 200 milliliters (ml) of absolute ethanol in a Parr shaker bottle wasadded 0.5 g of 5 percent palladium on charcoal. Hydrogen was passed overthe liquid surface using a Parr hydrogenator until ˜3 pounds (0.3 m) hadbeen consumed. The reaction mixture was filtered and the solvent removedby evaporation under reduced pressure. The residue was poured into asolution of 50 ml of water and 50 ml of 10 percent sodium hydroxide.This solution was extracted with methylene chloride. The extract waswashed with water, dried over magnesium sulfate and the solvent strippedaway from vacuum. The residue was heated at 0.02 millimeters of mercuryto 110° C. to remove lower boiling impurities. The above named productwas recovered as a pale yellow oil in a yield of 6.8 g and was ˜99percent pure. The Nuclear Magnetic Resonance spectrum (NMR) confirmedthe product. The product has a refractive index of n25/d=1.5946 and uponanalysis was found to have carbon, hydrogen and nitrogen contents of77.78, 5.56 and 4.92 percent, respectively, as compared with thetheoretical contents of 77.98, 5.24 and 5.05 percent, respectively, ascalculated for the above named compound (Compound 1).

EXAMPLE II 6-Ethoxy-2-(diphenoxymethyl)pyridine ##STR11##

To 30.0 ml of ethanol was added 1.10 g of sodium pellets. After thesodium had dissolved, 10.14 g of 6-chloro-2-(diphenoxymethyl)pyridine in50 ml of DMSO was added dropwise. The mixture was heated to 80° C. andheld there for 24 hours. The reaction was considered complete as seen bythe NMR. The reaction mixture was cooled, diluted with water andextracted with methyl chloroform. The organic layer was separated andwashed with water, dried over anhydrous magnesium sulfate, filtered andthe solvent removed by evaporation under reduced pressure. The crudeproduct was then distilled and the portion which distilled over at157°-165° C. at 0.05 millimeters of mercury was collected. The aboveindicated product was obtained in a yield of 8.95 g and was found tohave a refractive index of n26/d=1.5768. The NMR and Infrared Spectra(IR) were consistent with the structure for the above compound. Uponanalysis, the compound was found to have carbon, hydrogen and nitrogencontents of 74.56, 6.01 and 4.19 percent, respectively, as compared withthe theoretical contents of 74.77, 5.92 and 4.36 percent, respectively,as calculated for the above named compound (Compound 2).

EXAMPLE III 6-Methylthio-2-(diphenoxymethyl)pyridine ##STR12##

To a mixture of sodium methoxide (made from 100 ml (2.47 m) of methanoland 1.50 g (0.652 m) of sodium metal) which had been cooled to 13° C.was added 7.0 ml (0.126 m) of methylmercaptain. The mixture was allowedto warm to room temperature and then 20.0 g of6-chloro-2-(diphenoxymethyl)pyridine and 150 ml of dimethylsulfoxide wasadded thereto. The mixture was heated to 90° C. and after 4 days at thistemperature, the reaction mixture was cooled to room temperature andpoured into 300 ml of ice. The solution was extracted with methylenechloride and the extract was dried over magnesium sulfate and thesolvent stripped off under reduced pressure. The residue was furtherpurified using preparative high pressure liquid chromatography with a2:98 mixture of ethylacetate and hexane. The oil thus obtainedcrystallized in n-hexane and was purified by recrystallization fromn-hexane leaving the above named compound as a white solid in a yield of49 g (98 percent pure). The product melted at 58°-59° C. and itsstructure was confirmed by its NMR spectrum. Upon analysis, the productwas found to have carbon, hydrogen and nitrogen contents of 70.42, 5.19and 4.20 percent, respectively, as compared with the theoreticalcontents of 70.59, 5.26 and 4.33 percent, respectively, as calculatedfor the above named compound (Compound 3)

EXAMPLE IV 6-(2-Propenyloxy)-2-(diphenoxymethyl)pyridine ##STR13##

A solution of 5.0 g (0.17 m) of 6-hydroxy-2-(diphenoxymethyl)pyridine in35 ml of dimethylsulfoxide was slowly added to 0.49 g (0.020 m) of cleansodium hydride. After the evoluation of gas was completed, 1.8 ml ofallylbromide was added dropwise to the mixture. After a period of twohours, the reaction mixture was poured into 50 ml of water at 25° C. andthe mixture extracted with methylene chloride. The organic extract wasdried over magnesium sulfate and the solvent removed by evaporationunder reduced pressure. The residue was heated at 80° C. and 0.05 mm toremove low boiling impurities leaving 3.9 g of a light brown oil as theabove named product. The structure of product was confirmed by its NMR.The compound had a refractive index of n25/d=1.5828. Upon analysis, theproduct was found to have carbon, hydrogen and nitrogen contents of75.71, 5.91 and 4.13 percent, respectively, as compared with thetheoretical contents of 75.68, 5.71 and 4.20 percent, respectively, ascalculated for the above named compound (Compound 4).

EXAMPLE V O,O-DiethylO-(6-(diphenoxymethyl)-2-pyridinyl)phosphorothioate ##STR14##

To a mixture of 5.02 g (0.17 m) of6-hydroxy-2-(diphenoxymethyl)pyridine, 5.04 g (0.037 m) of potassiumcarbonate in 50.0 ml of acetonitrile was slowly added 3.21 g (0.017 m)of diethylchlorothiophosphonate. The mixture was stirred for 31/2 hours.The solvent was then removed from the reaction mixture by evaporationunder reduced pressure. The residue was dissolved in ether and filtered.The ether solution was washed with 5 percent sodium hydroxide and thenwith water. The ether layer was separated from the aqueous layer and theether layer was dried over anhydrous magnesium sulfate. The ether wasremoved by evaporation leaving 6.7 g of the above indicated product as ayellow oil and in a purity of 98 percent. The product had a refractiveindex of n26/d=1.5660. The structure of the product was confirmed by itsNMR. Upon analysis, the product was found to have carbon, hydrogen andnitrogen contents of 58.92, 5.35 and 2.95 percent, respectively, ascompared with the theoretical contents of 59.33, 5.39 and 3.15 percent,respectively, calculated for the above named compound (Compound 5).

EXAMPLE VI 6-(Diphenoxymethyl)-2-pyridinenitrile (K-153705) ##STR15##

A mixture of 4.18 g of 6-cyano-2-(dichloromethyl)pyridine, 5.25 g ofphenol, 3.33 g of potassium hydroxide and 50 ml of dimethylsulfoxide washeated to 60° C. After a reaction period of about 4 hours, the reactionwas complete. The mixture was cooled and poured into 100 ml of water andthen extracted with methylene chloride. The solvent extract was runthrough a bed of silica gel and the solvent removed. The mixture washeated to 160° C. at 0.05 milliliters of mercury. The resulting materialwas dissolved in a mixture of about 50 ml of methylene chloride filteredand the solvent removed by evaporation under reduced pressure. The abovenamed product was recovered in a yield of 0.95 g and melted at 82°-85°C. The structure of the product was confirmed by its NMR and IRspectrum. Upon analysis, the product was found to have carbon, hydrogenand nitrogen contents of 74.44, 4.72 and 9.05 percent, respectively ascompared with the theoretical contents of 75.50, 4.64 and 9.27 percent,respectively as calculated for the above named compound (Compound 28).

EXAMPLE VII 6-aminomethyl-2-(diphenoxymethyl)pyridine ##STR16##

To a solution of 0.81 g of 95 percent lithium aluminum hydride in 25 mlof ether was slowly added a solution of 5.90 g of6-cyano-2-(diphenoxymethyl)pyridine in 60 ml of ether so as to maintaina gentle reflux. The mixture was allowed to stir for about 4 hours. Anadditional 0.2-0.3 g of lithium aluminum hydride was added. Since noadditional reaction occured, 5 ml of water, 5 ml of 15 percent sodiumhydroxide and 20 ml of water were added consecutively. The reactionmixture was filtered and the organic portion separated. The aqueousportion was washed with ether and the combined organic portions weredried over magnesium sulfate. The solvent was stripped off and theresidue was dissolved in methylene chloride and then diluted with ˜900ml of hexane. The solution was passed through a silica gel column andthe silica gel was rinsed with methylene chloride and then withmethanol. The methanol was stripped off leaving the above named productin a yield of 3.0 grams. The structure of the product was confirmed byits NMR and IR Spectrum. Upon analysis, the product was found to havecarbon, hydrogen and nitrogen contents of 72.44, 5.92 and 8.82 percent,respectively as compared with the theoretical contents of 74.51, 5.88and 9.15 percent, respectively as calculated for the above namedcompound (Compound 30).

By following the appropriate preparative procedures as outlinedhereinabove and in the above example and employing the appropriatestarting materials, the following compounds set forth below in Table Ican be prepared.

                                      TABLE I                                     __________________________________________________________________________     ##STR17##                                                                                                 Analysis                                         Compound                     Calculated                                                                             Found    Physical Property              Number                                                                              R           X.sub.n                                                                           Z.sub.m                                                                              C  H  N  C  H  N  RI or MP                       __________________________________________________________________________     6    OCH.sub.3   H   H      74.27                                                                            5.54                                                                             4.56                                                                             73.78                                                                            5.39                                                                             4.50                                                                             1.5860                          7    OC.sub.2 H.sub.5                                                                          3-F 3-Cl                                                     8    OC.sub.2 H.sub.5                                                                          4-Cl                                                                              4-SCH.sub.3                                              9    OCHF.sub.2  H   H      66.47                                                                            4.37                                                                             4.08                                                                             66.23                                                                            4.30                                                                             3.99                                                                             1.5556                         10    OCH.sub.3   5-Cl                                                                              H                                                       11    morpholino  H   H      72.93                                                                            6.07                                                                             7.73                                                                             71.33                                                                            6.13                                                                             7.85                                                                             88°-91°          12    CH.sub.3    3-Br                                                                              4-n-OC.sub.4 H.sub.9                                    13    OC.sub.4 H.sub.9                                                                          H   H      75.64                                                                            6.59                                                                             4.01                                                                             75.42                                                                            6.63                                                                             3.90                                                                             1.5639                         14    piperidinyl H   H      76.67                                                                            6.67                                                                             7.78                                                                             75.51                                                                            6.69                                                                             7.58                                                                             bpt 180°-190°                                                    C. at                                                                        0.02 mm                        15    OCH(CH.sub.3).sub.2                                                                       H   H      75.22                                                                            6.27                                                                             4.18                                                                             74.84                                                                            6.18                                                                             4.11                                                                             1.5690                         16    N(CH.sub.3).sub.2                                                                         H   5-n-SC.sub.4 H.sub.9                                    17    CH.sub.3    H   H      78.35                                                                            5.84                                                                             4.81                                                                             77.80                                                                            5.93                                                                             4.93                                                                             63°-66°          18    OC.sub.2 H.sub.4 OH                                                                       H   H      71.22                                                                            5.64                                                                             4.15                                                                             70.93                                                                            5.75                                                                             4.04                                                                             1.5894                         19    Si-C.sub.4 H.sub.9                                                                        4-Cl                                                                              5-n-SC.sub.4 H.sub.9                                    20    OC.sub.2 H.sub.4 OCH.sub.3                                                                H   H      71.79                                                                            5.98                                                                             3.99                                                                             71.36                                                                            5.96                                                                             3.92                                                                             1.5717                         21    OCH.sub.2 OCH.sub.3                                                                       5-F 3-OCH.sub.3                                             22                                                                                   ##STR18##  4-Cl                                                                              4-Cl                                                    23    OCH(CH.sub.3)COOH                                                                         H   H      69.04                                                                            5.21                                                                             3.84                                                                             64.74                                                                            5.01                                                                             3.44                                                                             1.5682                         24    OCH(CH.sub.3)COOC.sub.2 H.sub.5                                                           H   H      70.23                                                                            5.85                                                                             3.56                                                                             69.51                                                                            5.80                                                                             3.24                                                                             1.5592                         25    triazolyl   H   H      69.77                                                                            4.65                                                                             16.28                                                                            70.58                                                                            4.69                                                                             14.87                                                                            65°-70° C.       26    NH(n-C.sub.6 H.sub.13)                                                                    H   H      76.60                                                                            7.45                                                                             7.45                                                                             75.71                                                                            7.44                                                                             7.27                                                                             1.5737                         27    SCH(CH.sub.3)COOH                                                                         H   2-SCH.sub.3                                             29    OCHCl.sub.2 H   H      62.29                                                                            4.27                                                                             3.59                                                                             60.64                                                                            3.99                                                                             3.72                              __________________________________________________________________________

PREPARATION OF STARTING MATERIALS

Those compounds employed as starting materials and which correspond tothe formula ##STR19## wherein Z and m are as hereinabove defined areknown compounds and can be prepared as taught in U.S. Pat. Nos.4,324,896 and 4,349,680.

Those compounds employed as starting materials and which correspond tothe formula ##STR20## wherein X, n, Z and m are as hereinabove definedcan be prepared by processes analogous to those taught in U.S. Pat. Nos.4,324,896 and 4,349,680 wherein one mole of an appropriate6-halo-2-(dichloromethyl)pyridine is reacted with 2 moles of anappropriate phenol.

The 6-halo-2-(dichloromethyl)pyridines employed as starting materialsare known compounds and can be prepared as taught in U.S. Pat. No.3,838,159. For those compounds wherein X is fluoro or chloro, thecompounds can also be prepared as taught in U.S. Pat. No. 3,687,827.

In accordance with the present invention, it has been discovered thatthe diphenoxymethylpyridine compounds of the present invention areuseful as pre- and post-emergent herbicides. In accordance with thisinvention, a method for controlling or inhibiting the growth ofundesirable plant species is provided which comprises applying toplants, plant parts or their habitat, an effective or growth inhibitingto herbicidally effective amount of at least one of the compounds as setforth hereinabove.

An outstanding feature of the present invention is the ability of thepresently claimed compounds to control, either by post-emergent orpre-emergent application, the growth of one or more of the grasses andbroadleaf plants, such as, for examle, barnyard grass, crabgrass, yellowfoxtail, wild oats, pigweed, cotton, velvet leaf, morning glory andyellow nutsedge.

The application of the compounds of the present invention to plants andplant parts and their habitats, gives rise to varying degrees ofresponse to the compounds depending upon the nature of the plant orseed, the stage of growth or maturity of the plant, the specificcompound employed, and the dosage at which plant or plant part orhabitat exposure to the compund is carried out, as well as environmentalconditions.

The minimum amount of active compound applied should be that which iseffective in controlling and/or killing undesirable plant growth.Ordinarily, for pre-emergent control, good results are obtained whenfrom 0.06 to 4 pounds or more of at least one of the active compoundsare applied per acre. In foliage treatment, good results are obtainedwhen from 0.02 to 4 pounds of active compound per acre are employed. Inselective applications to foliage for the control of many undesirableweeds in the presence of desired crop plants, a uniform dosage of fromabout 0.02 to 2 pounds of active compound can be employed.

The present invention can be carried out by directly employing theclaimed compounds singly or in combination with each other. However, thepresent invention also embraces the employment of liquid, granular,encapsulated or dust compositions containing at least one of saidcompounds. In such usage, the compound or compounds can be modified withone or more of a plurality of chemically inert additaments or pesticidalmaterials including solvents or other liquid carriers, surface activedispersing agents or coarsely or finely divided inert solids. Theaugmented compositions are also adapted to be employed as concentratesand subsequently diluted with additional inert carrier to produce othercompositions in the form of dusts, sprays, granules, washes or drenches.In compositions where the additament is a coarsely or finely dividedsolid, a surface active agent or the combination of a surface activeagent and a liquid additament, the added material cooperates with theactive component so as to facilitate the invention. Whether thecomposition is employed in liquid form, as a wettable powder, or as agranular or encapsulted material, the active compound will normally bepresent in an amount of from about 5 to about 95 percent by weight ofthe total composition.

In the preparation of dust compositions, the toxicant products can becompounded with any of the finely divided solids, such as, for example,pyrophyllite, talc, chalk, gypsum, fuller's earth, bentonite,attapulgite, and the like. In such operations, the finely dividedcarrier is ground or mixed with the toxicant or wet with a solution ofthe toxicant in a volatile organic solvent. Also, such dust compositionswhen employed as concentrates can be dispersed in water, with or withoutthe aid of dispersing agents to form spray mixtures.

Granular formulations are usually prepared by impregnating a solution ofthe toxicant in a volatile organic solvent onto a bed of coarselydivided clays such as, for example, attapulgite, bentonite, diatomite,or the like.

Similarly, the toxicant products can be compounded with a suitablewater-immiscible organic liquid and a surface active dispersing agent toproduce an emsulsifiable concentrate which can be further diluted withwater and oil to form spray mixtures in the form of oil-in-wateremulsions. In such compositions, the carrier comprises an aqueousemulsion, i.e., a mixture of water-immiscible solvent, emulsifying agentand water. Preferred dispersing agents which can be employed in thesecompositions, are oil-soluble materials including non-ionic emulsifierssuch as, for example, the condensation products of alkylene oxides withthe inorganic acids, polyoxyethylene derivatives or sorbitan esters,complex, ether alcohols and the like. Also, oil-soluble ionicemulsifying agents such as mahogany soaps can be used. Suitable organicliquids which can be employed in the composition include, for example,petroleum oils and distillates, toluene, liquid halohydrocarbons andsynthetic organic oils. The surface-active dispersing agents are usuallyemployed in liquid compositions and in the amount of from 0.1 to 20percent by weight of the combined weight of the dispersing agent andactive compound.

In addition, other liquid compositions containing the desired amount ofeffective agent can be prepared by dissolving the toxicant in an organicliquid such as, for example, acetone, methylene chloride, chlorobenzeneand petroleum distillates. The preferred organic solvent carriers arethose which are adapted to accomplish the penetration and impregnationof the environment and particularly soil with the toxicant compounds andare of such volatility as to leave little permanent residue thereon.Particularly desirable carriers are the petroleum distillates boilingalmost entirely under 400° F. at atmospheric pressure and having a flashpoint about 80° F. The proportion of the compounds of this inventionemployed in a suitable solvent may vary from about 2 to about 50 percentor higher.

In further embodiments, the compounds as employed in accordance with thepresent invention, or compositions containing the same, can beadvantageously employed in the present invention in combination with oneor more pesticidal or preservative compounds. In such embodiments, thepesticidal or preservative compound is employed either as a supplementaltoxicant or as an additament. Representative operable pesticidal orpreservative compounds include substituted phenols, cresols, substitutedcresols and their metal salts, bisphenols and thiobisphenols;halogenated salicylanilides, organo sulfur compounds, carbamatecompounds, quaternary ammonium compounds, organometallic compounds,inorganic salts and miscellaneous other compounds, such as phenol,cresol, trichlorophenols, tetrachlorophenols, pentachlorophenol,P-chloro-m-cresol, sodium pentachlorophenol and other sodium potassium,etc. salts of the phenols, substituted phenols, cresols and substitutedcresols, di- and tribrominated salicylanilides,2,2'-methylenebis(3,4,6-trichlorophenol),2,2'-thiobis(4,6-dichlorophenoxide), halogenated trifluoromethylsalicylanilide, disodium ethylenebisthiocarbamate, sodiumN-methyldithiocarbamate, zinc dimethyldithiocarbamate,2-mercaptobenzothiazole,3,5-dimethyltetrahydro-1,3,5-2H-thioadiazine-2-thione,2,3-dinitro-1,4-dithia-anthraquinone, dodecyl pyridinium chloride, alkyldimethylbenzylammonium chloride, dialkyl dimethylammonium chloride,bis-tributyltin oxide, bistripropyltin oxide, copper pentachlorophenate,copper 8-hydroxyquinolate, sodium borate, 9-undecylenic acid,10,10'-oxybisphenoxarsine,1-(3-chloroallyl)-3,5,7-triaza-1-azonia-adamantane chloride,1,4-bromobisacetobutene and substituted phosphorothioates (soil appliedinsecticides).

In application to an area to be treated, the compounds of this inventionmay be applied by spraying or by the use of mechanical spreaders inaccordance with conventional practice. With respect to application,however, it will be noted that, depending upon the particularcircumstances encountered, one method of application may be preferablyover others. Thus, for example, for preferred pre-emergence applicationit has been found very satisfactory to apply the active compound in aliquid spray or on granules and incorporate it into the soil.

In a further method, the distribution can be accomplished by introducinga toxicant or toxicants into the water employed to irrigate the soil. Inthis method, the amount of water can be varied in accordance with themoisture equivalent or field capacity of the soil in order to obtain thedesired depth of distribution of the toxicant.

The following embodiments are illustrative of the present methods.

EXAMPLE VII

Forty-five parts by weight of6-ethoxy-3-fluoro-2-(bis(3-chlorophenoxy)methylpyridine is mixed andground with 5 parts by weigh of Triton X-155 surfactant (an alkylatedaryl polyether alcohol) to prepare a water-dispersible concentratecomposition containing 90 percent by weight of the ester compound.

In a further operation, 25 parts by weight of6-methyl-3-bromo-2-(bis(4-n-butoxyphenoxy)methyl)pyridine, 10 parts byweight of Triton X-155 surfactant and 65 parts by weight of xylene aremixed together to prepare an emulsifiable concentrate compositioncontaining 25 percent by weight of said ester compound.

A mixture of 10 parts by weight of6-dimethylamino-2-(bis(5-n-butylthiophenoxy)methyl)pyridine, 10 parts byweight of O,O-di-n-butyl-4-chloroO-(bis(4-chlorophenoxy)methyl)o-2-pyridinyl)phosphorothioate, 0.1 partof Nacconol NR detergent (alkyl sulfonate), 0.1 part of Daxad No. 27 (apolymerized sodium salt of benzoid alkyl sulfonic acids) and 200 partsof water are ball-milled together to prepare a water-dispersible liquidconcentrate composition containing 20 parts by weight of the mixedpyridine compounds. The concentrate compositions thus prepared can bedispersed in water to prepare aqueous compositions which have verydesirable wetting and penetrating properties and are adapted todistribute growth inhibiting amounts of the diphenoxymethylpyridinecompounds on plant parts.

EXAMPLE VIII

Representative products of the present invention were evaluated for thepost-emergent control of barnyard grass, wild oats, crabgrass, pigweed,yellow foxtail and cotton. In these evaluations, plots of the aboveplant species grown to a height of about 4 inches were used. Aqueousspray compositions, each containing 4,000 parts of a givendiphenoxymethyl pyridine compound per million parts of ultimatecomposition, were prepared by admixing a predetermined amount of thediphenoxymethyl pyridine with a predetermined amount of awater-surfactant mixture to give an aqueous dispersion containing 4,000parts of the compound per million parts of the ultimate dispersion. Eachseparate composition was applied to a separate plot. The application wasmade to the point of run-off and was carried out with conventionalspraying equipment. Other plots were sprayed with similar compositionscontaining no toxicant to serve as controls. Thereafter, the plots weremaintained under conditions conducive for plant growth. Two weeks aftertreatment, the plots were examined for plant growth and evaluated. Theresults of the examination of the treated plots are set forth below inTable A.

                                      TABLE A                                     __________________________________________________________________________              Percent Kill and Control of                                         Compound Number                                                                         Barnyard Grass                                                                        Wild Oats                                                                           Crabgrass                                                                           Pigweed                                                                            Yellow Foxtail                                                                        Cotton                             __________________________________________________________________________    2         95      100   95    NT   95      100                                3         100     100   95    NT   95      90                                 4         100     100   70    100  --      90                                 6         100     100   99    --   90      NT                                 9         100     100   100   NT   100     100                                10        80       70   70    --   70      --                                 13        90      100   95    NT   80      100                                17        75      --    100   100  100     --                                 20        90      100   90     90  --      70                                 28        90       90   100   NT   --      80                                 __________________________________________________________________________     NT = Not Tested                                                          

In other operations carried out employing substantially the sameprocedures as in Example VIII, it was found that compound 15 gave 100percent kill and control of barnyard grass and pigweeds; compounds 29and 30 gave 100 percent kill and control of pigweeds; compounds 11 and29 were found to give at least 70 percent kill and control of crabgrass;compound 18 was found to give at least 80 percent kill and control ofwild oats and compounds 14, 18 and 20 were found to give at least 80percent kill and control of cotton plants.

EXAMPLE IX

Additional products of the present invention were evaluated for thepost-emergent control of morning glory and velvet leaf. In theseevaluations, plots of the above plant species grown to a height of about4 inches were used. Aqueous spray compositions, each containing 4,000parts of a given diphenoxymethyl pyridines compound per million parts ofultimate composition, were prepared in accordance with the procedures ofExample VIII, and each separate composition was applied to a separateplot. The application was made to the point of run-off and was carriedout with conventional spraying equipment. Other plots were sprayed withsimilar compositions containing no toxicant to serve as controls.Thereafter, the plots were maintained under conditions conducive forplant growth. Two weeks after treatment, the plots were examined forplant growth and evaluated. It was found that each of compounds 2, 6, 9,10, 13, 18, 20, 26, 28 and 29 gave at least 70 percent kill and controlof morning glory and each of componds 2, 3, 9, 10 and 29 gave at least80 percent kill and control of velvet leaf.

EXAMPLE X

Aqueous compositions of various ester compounds prepared in accordancewith Example VIII were employed for pre-emergent applications on plotsimmediately after they were seeded with crabgrass, wild oats, barnyardgrass, pigweed and yellow foxtail. Other plots similarly seeded with theabove plant species were treated with like compositions containing notoxicant to serve as control plots. The treating applications werecarried out by drenching the soil with the aqueous compositions toobtain a treating rate of 10 pounds per acre. Thereafter, the plots weremaintained under conditions conducive for good plant growth. Two weeksafter treatment, the plots were examined to determine the percent plantgrowth and evaluated. The results of the examinations are set forthbelow in Table B.

                                      TABLE B                                     __________________________________________________________________________              Percent Kill and Control of                                         Compound Number                                                                         Barnyard Grass                                                                        Crabgrass                                                                           Yellow Foxtail                                                                        Wild Oats                                                                           Pigweed                                 __________________________________________________________________________    1         100     100    80     --    NT                                      2         100     100   100     100   100                                     3         100     100   100      80   100                                     4         100     100    90     100   100                                     6         100     100   100     100   100                                     9         100     100   100     100   100                                     13         75     100   --       80   100                                     15         90     --     80      90   --                                      17        100     100   100     100   100                                     20        100     100   100     100   100                                     24         95      95    70      98   NT                                      25        --       95    80     --    100                                     28        100     100   100     100   100                                     __________________________________________________________________________     NT = Not Tested                                                          

In other operations carried out employing substantially the sameprocedures as in Example IX, it was found that compounds 5 and 11 gave100 percent kill and control of crabgrass and compounds 11 and 23 gave100 percent kill and control of pigweeds.

EXAMPLE XI

Aqueous compositions of various compounds prepared in a manner similarto that of Example VIII were employed for a pre-emergent applications onplots immediately after their being seeded with seeds of morning gloryand velvet leaf. Other plots similarly to be seeded with the above plantspecies were treated with the like compositions containing no toxicantto serve as control plots. The treating applications were carried out bydrenching the soil with the aqueous compositions to a depth of about oneinch to obtain a treating rate of 10 pounds per acre. Thereafter, theplots were maintained under conditions conducive for good plant growth.Two weeks after treatment, the plots were examined to determine thepercent plant growth and evaluated. It was found that compounds 2, 4, 6,23 and 28 gave 100 percent kill and control of morning glory; compounds4, 6, 9, and 28 gave 100 percent kill and control of velvet leaf andcompounds 2, 3 and 20 gave at least 75 percent kill and control ofvelvet leaf.

PREPARATION OF STARTING MATERIALS

Those compounds employed as starting materials which correspond to theformula ##STR21## wherein X, z and m are as defined hereinabove are allknown compounds and can be prepared as taught in U.S. Pat. No.4,324,896, U.S. Pat. No. 4,349,680 and U.S. Pat. No. 4,351,943.

Those compounds employed as starting materials which correspond to theformula ##STR22## wherein X, n, Z and m are hereinbefore defined can beprepared in substantially the same manner as set forth directly aboveemploying the appropriate substituted-2-(dichloromethyl)pyridine whichare taught in U.S. Pat. Nos. 3,687,827 and 3,838,159.

Those compounds employed as starting materials which correspond to theformula ##STR23## can be prepared by the reaction of an appropriate6-halo-2-((diphenoxy or substituted diphenoxy)methyl)pyridine witheither an alkali metal hydroxide or mercaptide such as the sodium orpotassium compounds (depending on whether A is oxygen or sulfur) in thepresence of a solvent such as dimethylsulfoxide at a temperature of fromabout 80° to about 150° C. for from about 1 to 16 hours. After thecompletion of the reaction, the reaction mixture is diluted with waterand extracted with a solvent such as trichloroethane. The aqueous layeris then acidified to about a pH 1 with concentrated hydrochloric acidand extracted with trichloroethane. The organic portions are combined,washed with water, dried and the solvent is removed to give the desiredproduct.

What is claimed is:
 1. A compound corresponding to the formulawherein Rrepresents cyano; X represents bromo, chloro or fluoro; n represnts aninteger of 0 or 1; Z represents bromo, chloro, fluoro, alkylthio of 1 to4 carbon atoms or alkoxy of 1 to 4 carbon atoms and m represents aninteger of 0 or
 1. 2. The compound as defined in claim 1 which is6-cyano-2-(diphenoxymethyl)pyridine.
 3. A herbicidal composition whichcomprises an inert carrier in admixture with a herbicidally effectiveamount of a compound corresponding to the formula ##STR24## wherein Rrepresents cyano; X represents bromo, chloro or fluoro; n represents aninteger of 0 or 1; Z represents bromo, chloro, fluoro, alkylthio of 1 to4 carbon atoms or alkoxy of 1 to 4 carbon atoms and m represents aninteger of 0 or
 1. 4. The composition as defined in claim 3 wherein thecompound is 6-cyano-2-(diphenoxymethyl)pyridine.
 5. A method forcontrolling the growth of undesirable plants which comprises applying toplants, plant parts or their habitat a composition which comprises aninert carrier in admixture with a herbicidally effectiver amount of acompound corresponding to the formula ##STR25## wherein R representscyano; X represents bromo, chloro or fluoro; n represents an integer of0 or 1; Z represents bromo, chloro, fluoro, alkylthio of 1 to 4 carbonatoms or alkoxy of 1 to 4 carbon atoms and m represents an integer of 0or
 1. 6. The method as defined in claim 5 wherein the compound is6-cyano-2-(diphenoxymethyl)pyridine.